Homogeneous Hydrogenation of Esters Employing a Complex of Iron as Catalyst

a technology of complexes and iron, applied in the preparation of oxygen-containing compounds, organic compounds/hydrides/coordination complexes, physical/chemical process catalysts, etc., can solve the problems of high energy and capital expenditure of processes, and achieve the effect of reducing or minimizing the generation of harmful wastes

Inactive Publication Date: 2015-10-01
THE PROCTER & GAMBLE COMPANY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0005]The present invention provides a homogeneous method for the hydrogenation of esters under relatively mild conditions by employing molecular catalysts based on iron, which is an earth abundant and environmentally benign metal. The method is well-suited for catalyzing the hydrogenation of a wide variety of organic carbonyls without generating non-alcohol byproducts. The homogeneous method comprises contacting organic carbonyls with molecular hydrogen (H2) in the presence of the iron-based catalyst. Further, the method is effective for the conversion of refined oils, such as coconut or palm, directly to detergent-length alcohols without the addition of solvent (“neat”) thus eliminating or minimizing the generation of harmful wastes.

Problems solved by technology

While effective, these processes are very energy and capital intensive.

Method used

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  • Homogeneous Hydrogenation of Esters Employing a Complex of Iron as Catalyst
  • Homogeneous Hydrogenation of Esters Employing a Complex of Iron as Catalyst
  • Homogeneous Hydrogenation of Esters Employing a Complex of Iron as Catalyst

Examples

Experimental program
Comparison scheme
Effect test

example 1

Catalyst Synthesis

Example 1A

Synthesis of [iPrPN(H)P]Fe(CO)Br2 (Formula 6)

[0020]In a glovebox, a 100 mL oven-dried Schlenk flask equipped with a stir bar was charged with anhydrous FeBr2 (510 mg, 2.36 mmol) and 30 mL of THF, which resulted in an orange solution. A THF solution of (iPr2PCH2CH2)NH (10 wt %, 9.0 mL, 2.60 mmol) was added and, upon mixing with the FeBr2 solution for a few minutes, a thick white precipitate formed. The flask was connected to a Schlenk line, and the argon inside the flask was replaced with CO by performing a freeze-pump-thaw cycle. When mixed with CO and warmed to room temperature, the white precipitate quickly dissolved to yield a deep blue solution. The solution was stirred under 15 psig of CO for 1 h followed by evaporation to dryness under vacuum. The resulting blue residue was washed with pentane (15 mL×3) and dried under vacuum to give the titled compound as a blue powder (1.20 g, 93% yield). The 1H NMR spectra of this complex showed broad resonances,...

example 1b

Synthesis of [iPrPN(H)P]Fe(H)(CO)(BH4) (Formula 2)

[0021]Under an argon atmosphere, a 100 mL oven-dried Schlenk flask equipped with a stir bar was charged with Formula 6 (400 mg, 0.73 mmol) and NaBH4 (138 mg, 3.65 mmol). Adding 50 mL of dry and degassed ethanol to this mixture at 0° C. at first resulted in a green solution, which changed its color to yellow within a few minutes. The resulting mixture was gradually warmed to room temperature and then stirred for additional 16 h. Removal of the volatiles under vacuum afforded a yellow solid, which was treated with 80 mL of toluene and then filtered through a pad of Celite to give a yellow solution. Evaporating the solvent under vacuum yielded the desired compound as a bright yellow powder (250 mg, 85% yield). This compound can be exposed to air briefly without significant decomposition.

[0022][iPrPN(H)P]Fe(D)(CO)(BD4) (Formula 2-d5) were synthesized similarly from Formula 6 and NaBD4. 1H NMR (400 MHz, C6D6, δ): −19.52 (t, JP-H=50.4 Hz, ...

example 1c

Synthesis of [iPrPN(H)P]Fe(H)(CO)(Br) (Formula 7)

[0023]Under an argon atmosphere, a 100 mL oven-dried Schlenk flask equipped with a stir bar was charged with Formula 6 (100 mg, 0.182 mmol) and NaBH4 (7.0 mg, 0.185 mmol). Adding 15 mL of dry and degassed ethanol to this mixture at 0° C. at first resulted in a green solution, which changed its color to orange within a few minutes. The resulting mixture was gradually warmed to room temperature and then stirred for additional 16 h. Removal of the volatiles under vacuum afforded an orange solid, which was treated with 40 mL of toluene and then filtered through a pad of Celite to give an orange solution. After the solution was concentrated to ˜3 mL under vacuum, it was carefully layered with ˜10 mL of pentane and placed in a refrigerator (0° C.). Orange crystals of the desired compound formed within a day. Decantation of the top layer using a cannula followed by solvent evaporation afforded the titled compound (60 mg, 70% yield). This com...

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Abstract

The homogeneous hydrogenation of organic carbonyls, especially esters, under relatively mild conditions using iron hydrido-borohydride catalyst complexes having amino-phosphine pincer ligands. The catalyst and process are well-suited for catalyzing the hydrogenation of a wide variety of organic carbonyls, such as hydrogenation of fatty acid esters to alcohols. In particular embodiments, the process can be carried out in the absence of solvent.

Description

FIELD OF THE INVENTION[0001]The present invention relates to a homogenous process for the hydrogenation of organic carbonyl compounds.BACKGROUND OF THE INVENTION[0002]Hydrogenation of esters is an industrially important process and is used to manufacture alcohols on a multi-million ton scale per annum for numerous applications. Long-chain or fatty alcohols, in particular, are widely used as precursors to surfactants, plasticizers, and solvents. In 2012, world consumption of fatty alcohols grew to 2.2 million metric tons, and the global demand was projected to increase at a compound annual growth rate of 3-4% from 2012 to 2020. Currently, about 50% of fatty alcohols are considered “natural fatty alcohols” as they are produced through hydrogenation of fatty acid methyl esters that are derived from coconut and palm kernel oils, among other renewable materials.[0003]Current technologies for the large scale ester hydrogenation to fatty alcohols (e.g. detergent length methyl esters, prima...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C07C29/149B01J31/16B01J31/20B01J31/24B01J31/22
CPCC07C29/149B01J31/2476B01J31/2295B01J2531/842B01J31/16B01J2231/64B01J2231/643B01J31/20C07C37/00C07C41/26B01J2531/0244C07C33/22C07C33/20C07C33/46C07C31/125C07C31/135C07C43/23C07C39/08C07C31/207
Inventor FAIRWEATHER, NEIL THOMASGIBSON, MICHAEL STEVENGUAN, HAIRONGCHAKRABORTY, SUMITDAI, HUIGUANGBHATTACHARYA, PAPRI
Owner THE PROCTER & GAMBLE COMPANY
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